We have synthesized two poly(p-phenylene vinylene) (PPV) derivatives. The first one consists of a copolymer formed by a random succession of phenylene vinylene and ether groups and the second one is characterized by a pendant side chain containing ether groups hereafter referred to as polyXI and C8-PPV respectively. The polymer's chemical structures were characterized by 1 3 C solid state NMR, FTIR and microanalysis.Thermal and structural properties were studied by differential scanning calorimetry and X-ray diffraction. The results were compared to pristine PPV. The effect of pendant side chain was discussed. Moreover, spectroscopic properties were investigated by means of photoluminescence and electron paramagnetic resonance and correlated to the material structure. From these studies we were able to present a possible explanation for the C8-PPV insolubility.